ES2215204T3 - PROCEDURE FOR THE PREPARATION OF ARYLAMIDES OF HETEROAROMATIC CARBOXYLIC ACIDS. - Google Patents
PROCEDURE FOR THE PREPARATION OF ARYLAMIDES OF HETEROAROMATIC CARBOXYLIC ACIDS.Info
- Publication number
- ES2215204T3 ES2215204T3 ES97105060T ES97105060T ES2215204T3 ES 2215204 T3 ES2215204 T3 ES 2215204T3 ES 97105060 T ES97105060 T ES 97105060T ES 97105060 T ES97105060 T ES 97105060T ES 2215204 T3 ES2215204 T3 ES 2215204T3
- Authority
- ES
- Spain
- Prior art keywords
- nitrogen
- formula
- sup
- phenyl
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 150000001735 carboxylic acids Chemical class 0.000 title description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 150000001408 amides Chemical class 0.000 claims description 12
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- -1 methoxy, methyl Chemical group 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 125000002541 furyl group Chemical group 0.000 claims description 3
- 125000001041 indolyl group Chemical group 0.000 claims description 3
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 3
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 3
- 125000001544 thienyl group Chemical group 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical group 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 3
- 150000007513 acids Chemical class 0.000 abstract description 2
- 239000004009 herbicide Substances 0.000 abstract description 2
- 150000004982 aromatic amines Chemical class 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000008096 xylene Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229910052763 palladium Inorganic materials 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000001072 heteroaryl group Chemical group 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 3
- 238000007327 hydrogenolysis reaction Methods 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- LFVNBAYLMRRFQM-UHFFFAOYSA-N 2-chloro-6-[3-(trifluoromethyl)phenoxy]pyridine Chemical compound FC(F)(F)C1=CC=CC(OC=2N=C(Cl)C=CC=2)=C1 LFVNBAYLMRRFQM-UHFFFAOYSA-N 0.000 description 2
- UGEJOEBBMPOJMT-UHFFFAOYSA-N 3-(trifluoromethyl)phenol Chemical compound OC1=CC=CC(C(F)(F)F)=C1 UGEJOEBBMPOJMT-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 2
- 229940031826 phenolate Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- BINQYVWLAWZYPX-UHFFFAOYSA-N 1,3,5-triazine-2-carboxylic acid Chemical compound OC(=O)C1=NC=NC=N1 BINQYVWLAWZYPX-UHFFFAOYSA-N 0.000 description 1
- 125000003363 1,3,5-triazinyl group Chemical group N1=C(N=CN=C1)* 0.000 description 1
- MAKFMOSBBNKPMS-UHFFFAOYSA-N 2,3-dichloropyridine Chemical compound ClC1=CC=CN=C1Cl MAKFMOSBBNKPMS-UHFFFAOYSA-N 0.000 description 1
- CEPCPXLLFXPZGW-UHFFFAOYSA-N 2,4-difluoroaniline Chemical compound NC1=CC=C(F)C=C1F CEPCPXLLFXPZGW-UHFFFAOYSA-N 0.000 description 1
- FILKGCRCWDMBKA-UHFFFAOYSA-N 2,6-dichloropyridine Chemical compound ClC1=CC=CC(Cl)=N1 FILKGCRCWDMBKA-UHFFFAOYSA-N 0.000 description 1
- MFDBYHAXXAGPNF-UHFFFAOYSA-N 2-[3-(trifluoromethyl)phenoxy]pyridine Chemical compound FC(F)(F)C1=CC=CC(OC=2N=CC=CC=2)=C1 MFDBYHAXXAGPNF-UHFFFAOYSA-N 0.000 description 1
- JHFQIWDOKUTRBA-UHFFFAOYSA-N 3-chloro-2-[3-(trifluoromethyl)phenoxy]pyridine Chemical compound FC(F)(F)C1=CC=CC(OC=2C(=CC=CN=2)Cl)=C1 JHFQIWDOKUTRBA-UHFFFAOYSA-N 0.000 description 1
- KRZCOLNOCZKSDF-UHFFFAOYSA-N 4-fluoroaniline Chemical compound NC1=CC=C(F)C=C1 KRZCOLNOCZKSDF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- WYEHFWKAOXOVJD-UHFFFAOYSA-N diflufenican Chemical compound FC1=CC(F)=CC=C1NC(=O)C1=CC=CN=C1OC1=CC=CC(C(F)(F)F)=C1 WYEHFWKAOXOVJD-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/26—Radicals substituted by halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/61—Halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
- C07D213/643—2-Phenoxypyridines; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
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Abstract
SE DESCRIBE UN METODO PARA LA PREPARACION DE ARILAMIDAS DE ACIDOS CARBOXILICOS HETEROAROMATICOS DE FORMULA DONDE CADA A{SUP,N} ES NITROGENO O CR{SUP,N} (N = 1-5), CON LA CONDICION DE QUE AL MENOS UN MIEMBRO DEL ANILLO ES NITROGENO Y NO HAY DOS ATOMOS DE NITROGENO UNIDOS CONSECUTIVAMENTE; R{SUP,1} A R{SUP,5}, SI EXISTEN, SON INDEPENDIENTEMENTE HIDROGENO, ALQUILO O ARILO C{SUB,1-4}, DONDE UNO DE LOS SUSTITUYENTES R{SUP,1} A R{SUP,5} ES UN GRUPO DE FORMULA CO O HETEROAROMATICO EN SU CASO SUSTITUIDO; R{SUP,6} SIGNIFICA HIDROGENO O ALQUILO C{SUB,1-4} Y R{SUP,7} UN RADICAL AROMATICO O HETEROAROMATICO EN SU CASO SUSTITUIDO. LAS AMIDAS SE OBTIENEN A PARTIR DE LOS RESPECTIVOS COMPUESTOS HALOGENADOS HETEROAROMATICOS, LAS AMINAS AROMATICAS CORRESPONDIENTES Y MONOXIDO DE CARBONO EN PRESENCIA DE UN COMPLEJO DE PALADIODIFOSFINA. LOS COMPUESTOS DE ESTE TIPO SON HERBICIDAS IMPORTANTES.A METHOD IS DESCRIBED FOR THE PREPARATION OF ARYLAMIDS OF CARBOXYLIC HETEROAROMATIC ACIDS OF FORMULA WHERE EACH {SUP, N} IS NITROGEN OR CR {SUP, N} (N = 1-5), WITH THE CONDITION THAT AT LEAST ONE MEMBER OF RING IS NITROGEN AND THERE ARE NO TWO ATOMOS OF NITROGEN CONSEQUENTLY; R {SUP, 1} AR {SUP, 5}, IF THERE ARE, ARE INDEPENDENTLY HYDROGEN, RENT OR ARILO C {SUB, 1-4}, WHERE ONE OF THE SUBSTITUTES R {SUP, 1} AR {SUP, 5} EN A GROUP OF FORMULA CO OR HETEROAROMATICO IN ITS SUBSTITUTED CASE; R {SUP, 6} MEANS HYDROGEN OR RENT C {SUB, 1-4} AND R {SUP, 7} AN AROMATIC OR HETEROAROMATIC RADICAL IN THEIR SUBSTITUTED CASE. AMIDAS ARE OBTAINED FROM THE RESPECTING HETEROAROMATIC HALOGENATED COMPOUNDS, CORRESPONDING AROMATIC AMINES AND CARBON MONOXIDE IN THE PRESENCE OF A PALADYDIFOSPHINE COMPLEX. THE COMPOUNDS OF THIS TYPE ARE IMPORTANT HERBICIDES.
Description
Procedimiento para la preparación de arilamidas de ácidos carboxílicos heteroaromáticos.Procedure for the preparation of arylamides of heteroaromatic carboxylic acids.
La presente invención se refiere a un procedimiento para la preparación de arilamidas de ácidos carboxílicos heteroaromáticos, por reacción de compuestos halogenados heteroaromáticos con monóxido de carbono y aminas aromáticas, en presencia de un catalizador y una base.The present invention relates to a procedure for the preparation of acid arylamides heteroaromatic carboxylic acids, by reaction of compounds heteroaromatic halogenates with carbon monoxide and amines aromatic, in the presence of a catalyst and a base.
Las amidas preparadas según la invención poseen la fórmula generalThe amides prepared according to the invention have the general formula
en la cual significanin which mean
A^{1} nitrógeno o CR^{1},A 1 nitrogen or CR 1,
A^{2} nitrógeno o CR^{2},A 2 nitrogen or CR 2,
A^{3} nitrógeno o CR^{3},A 3 nitrogen or CR 3,
A^{4} nitrógeno o CR^{4},A 4 nitrogen or CR 4,
y A^{5} nitrógeno o CR^{5},and A 5 nitrogen or CR 5,
con la condición de que al menos uno de los miembros de anillo A^{1} a A^{5} es nitrógeno y que no estén unidos entre sí dos átomos de nitrógeno inmediatamente adyacentes,with the proviso that at least one of the ring members A 1 to A 5 is nitrogen and they are not joined together two nitrogen atoms immediately adjacent,
R^{1} hasta R^{5}, si están presentes, son, de forma independiente entre sí, hidrógeno, alquilo-C_{1-4} o arilo, siendo, sin embargo, uno de los sustituyentes R^{1} hasta R^{5} un grupo de la fórmula -OR, en la que R es un resto aromático o heteroaromático eventualmente sustituido,R 1 to R 5, if present, are, independently of each other, hydrogen, C 1-4 alkyl or aryl, being, however, one of the substituents R 1 to R 5 a group of the formula -OR, in which R is an aromatic moiety or optionally substituted heteroaromatic,
R^{6} es hidrógeno o alquilo-C_{1-4}, yR 6 is hydrogen or C 1-4 alkyl, and
R^{7} es un resto aromático o heteroaromático, eventualmente sustituido, al que pertenecen, en especial, las arilamidas de los ácidos piridín, pirimidín, pirazín y 1,3,5-triazin-carboxílicos.R 7 is an aromatic or heteroaromatic moiety, eventually replaced, to which they belong, especially arylamides of the acids pyridin, pyrimidin, pyrazin and 1,3,5-triazine carboxylic.
Numerosos compuestos de esta estructura, en especial aquéllos en los que uno de los sustituyentes R^{1} hasta R^{5} es un grupo ariloxi (-OR) adyacente a un átomo de nitrógeno de anillo, son importantes herbicidas (documentos WO-A 94/27974, EP-A 0 053 011, EP-A 0 447 004). La síntesis de estos compuestos conocidos se realiza habitualmente a partir de los correspondientes ácidos carboxílicos o derivados de ácidos carboxílico (cloruros ácidos, ésteres, nitrilos). No obstante, éstos son a menudo de difícil acceso y, por lo tanto, caros.Numerous compounds of this structure, in especially those in which one of the substituents R1 up to R 5 is an aryloxy group (-OR) adjacent to a nitrogen atom ring, are important herbicides (documents WO-A 94/27974, EP-A 0 053 011, EP-A 0 447 004). The synthesis of these compounds known is usually done from the corresponding carboxylic acids or carboxylic acid derivatives (chlorides acids, esters, nitriles). However, these are often from difficult access and therefore expensive.
Misión de la presente invención fue, por tanto, poner a disposición un procedimiento alternativo, a partir de eductos de más fácil acceso.Mission of the present invention was therefore make available an alternative procedure, from Eductos easier access.
De acuerdo con la invención, esta misión se resuelve por los procedimientos según las reivindicaciones 1 y 13.According to the invention, this mission is resolves by the procedures according to claims 1 and 13.
Se ha encontrado que compuestos halógenos de la fórmulaIt has been found that halogen compounds of the formula
en la que A^{1} hasta A^{5} tienen los significados anteriormente mencionados y X es cloro, bromo o yodo, reaccionan directamente con monóxido de carbono y una amina primaria o secundaria de la fórmula generalin which A 1 to A 5 have the meanings mentioned above and X is chlorine, bromine or iodine, react directly with carbon monoxide and a primary amine or secondary formula general
IIIR^{6}-NH-R^{7}IIIR 6 -NH-R 7
en la que R^{6} y R^{7} tienen los significados anteriormente mencionados, en presencia de una base, para formar los productos (1) deseados, con un rendimiento cuantitativo correcto a regular, cuando se utiliza como catalizador un complejo de paladio con una difosfina de la fórmula generalin which R 6 and R 7 have the aforementioned meanings, in the presence of a base, to form the desired products (1), with a yield correct quantitative to regulate, when used as a catalyst a palladium complex with a diphosphine of the formula general
IVR^{8}R^{9}P-[CH_{2}]_{n}-PR^{10}R^{11}IVR 8 R 9 P- [CH 2] n -PR 10 R 11
en la que significan R^{8} hasta R^{11}, de forma independiente entre sí, fenilo o fenilo sustituido y n, 3 ó 4.in which they mean R 8 to R 11, of independently of each other, substituted phenyl or phenyl and n, 3 or Four.
Tanto en estas definiciones como en lo sucesivo, se entiende por alquilo C_{1-4} todos los grupos alquilo lineales o ramificados, primarios, secundarios o terciarios, con hasta 4 átomos de carbono. Por restos aromáticos o heteroaromáticos se entienden en estas definiciones y en lo sucesivo, especialmente sistemas mono- o policíclicos tales como, por ejemplo, fenilo, naftilo, bifenililo, antracenilo, furilo, pirrolilo, pirazolilo, tiofenilo, piridilo, indolilo o quinolinilo. Éstos pueden portar uno o múltiples sustituyentes iguales o diferentes, por ejemplo, grupos alquilo inferiores tales como metilo, grupo alquilo halogenados tales como trifluorometilo, grupos alcoxi inferiores tales como metoxi, o grupos alquiltio- (alcanosulfonilo) o alcanosulfonilo tales como metiltio o etanosulfonilo. Por fenilo sustituido se entienden, en especial, grupos tales como (p)-fluorofenilo, (p)-metoxifenilo, (p)-tolilo o (p)-trifluorometilfenilo.In both these definitions and hereafter, C 1-4 alkyl is understood as meaning all linear or branched, primary, secondary or tertiary alkyl groups with up to 4 carbon atoms. By aromatic or heteroaromatic moieties are understood in these definitions and hereafter, especially mono- or polycyclic systems such as, for example, phenyl, naphthyl, biphenyl, anthracenyl, furyl, pyrrolyl, pyrazolyl, thiophenyl, pyridyl, indolyl or quinolinyl. These may carry one or multiple identical or different substituents, for example, lower alkyl groups such as methyl, halogenated alkyl groups such as trifluoromethyl, lower alkoxy groups such as methoxy, or alkylthio- (alkanesulfonyl) or alkanesulfonyl groups such as methylthio or ethanesulfonyl. Substituted phenyl means, in particular, groups such as ( p ) -fluorophenyl, ( p ) -methoxyphenyl, ( p ) -tolyl or ( p ) -trifluoromethylphenyl.
Los compuestos halogenados (II) que sirven como materiales de partida son compuestos conocidos, o se pueden preparar de manera análoga a los compuestos conocidos. Se describen numerosos compuestos de este tipo, por ejemplo, en los documentos US-A 4 254 125 y EP-A 0 001 187.Halogenated compounds (II) that serve as starting materials are known compounds, or they can be prepared analogously to known compounds. Numerous are described compounds of this type, for example, in documents US-A 4 254 125 and EP-A 0 001 187.
Aquellos compuestos halogenados (II) en los que los grupos de la fórmula -OR están unidos a uno de los átomos de carbono adyacentes al átomo de nitrógeno de anillo, se preparan convenientemente haciendo reaccionar un dihalogenuro de la fórmula generalThose halogenated compounds (II) in which the groups of the formula -OR are attached to one of the atoms of carbon adjacent to the ring nitrogen atom, are prepared conveniently reacting a dihalogenide of the formula general
en la cual A^{1} hasta A^{5} tienen los significados anteriormente mencionados, con la condición de que uno de los restos R^{1} hasta R^{5} en uno de los átomos de carbono adyacente a uno de los átomos de nitrógeno de anillo esté sustituido con Z, que significa cloro, bromo o yodo, y X signifique, de forma independiente, cloro, bromo o yodo, con un compuesto hidroxi aromático o heteroaromático de la fórmula generalin which A 1 to A 5 have the meanings mentioned above, on the condition that one of the R 1 to R 5 moieties on one of the carbon atoms adjacent to one of the ring nitrogen atoms be substituted with Z, which means chlorine, bromine or iodine, and X means, so independent, chlorine, bromine or iodine, with a hydroxy compound aromatic or heteroaromatic of the formula general
VIR-OHVIR-OH
en la que R tiene el significado anteriormente mencionado.in which R has the meaning above mentioned.
El procedimiento según la invención se adecua, preferentemente, para la preparación de amidas (I) en las que A^{2} significa nitrógeno y que forman con los restantes miembros del anillo un anillo de piridina. Se prefieren de forma especial las amidas (I) en las que R^{1} es un grupo de la fórmula -OR, en la que R tiene el significado anteriormente mencionado.The method according to the invention is suitable, preferably, for the preparation of amides (I) in which A 2 means nitrogen and they form with the remaining members from the ring a pyridine ring. Especially preferred are amides (I) in which R1 is a group of the formula -OR, in the that R has the aforementioned meaning.
De igual forma, se prefieren las amidas (I) en las que A^{1} significa nitrógeno y que forma con los restantes miembros del anillo un anillo de piridina,Similarly, amides (I) are preferred in those that A 1 means nitrogen and that forms with the remaining ring members a pyridine ring,
aquéllas en las que A^{1} y A^{5} significan nitrógeno y que forman con los restantes miembros del anillo un anillo de pirimidina,those in which A 1 and A 5 mean nitrogen and that form with the remaining ring members a pyrimidine ring,
aquéllas en las que A^{1} y A^{4} significan nitrógeno y que forman con los restantes miembros del anillo un anillo de pirazina,those in which A 1 and A 4 mean nitrogen and that form with the remaining ring members a pyrazine ring,
así como aquéllas en las que A^{1}, A^{3} y A^{5} significan nitrógeno y que forman con los restantes miembros del anillo un anillo de 1,3,5-triazina.as well as those in which A 1, A 3 and A 5 means nitrogen and they form with the remaining members of the ring a 1,3,5-triazine ring.
De las cuatro clases mencionadas en último lugar se prefieren especialmente, una vez más, aquellas amidas en las que R^{2} significa un grupo de la fórmula -OR, en la que R tiene el significado anteriormente mencionado.Of the four classes mentioned last Especially preferred, once again, are those amides in which R2 means a group of the formula -OR, in which R has the aforementioned meaning
Adicionalmente, de las amidas (I) se prefieren aquéllas en las que R es un grupo fenilo eventualmente sustituido. Esto es especialmente válido para las amidas anteriormente mencionadas con un anillo de piridina, pirimidina, pirazina o 1,3,5-triazina, en las que R^{1} o R^{2} es un grupo de la fórmula -OH.Additionally, of the amides (I) are preferred those in which R is an optionally substituted phenyl group. This is especially valid for the amides above. mentioned with a pyridine, pyrimidine, pyrazine or ring 1,3,5-triazine, in which R 1 or R 2 is a group of the formula -OH.
Se prefieren, igualmente, aquellas amidas en las que R^{6} significa hidrógeno y R^{7} significa un grupo fenilo eventualmente sustituido.Also preferred are those amides in the that R 6 means hydrogen and R 7 means a phenyl group eventually replaced.
Como compuestos halogenados (II) se prefieren los compuestos de cloro (X = Cl).Halogenated compounds (II) are preferred chlorine compounds (X = Cl).
El complejo de paladio-difosfina, con acción catalítica, se forma convenientemente in situ, haciendo reaccionar paladio en forma elemental y finamente distribuida (por ejemplo, paladio sobre carbono activo), una sal de Pd(II) (por ejemplo, cloruro o acetato), o un complejo adecuado de Pd(II) (por ejemplo, dicloro-bis(trifenilfosfin)-paladio (II), con difosfina. Preferentemente, paladio se utiliza en una cantidad de 0,02 hasta 0,2% en moles de Pd(II), o 0,5 hasta 2% en moles (Pd(0) (como Pd/C), siempre referido al compuesto halogenado (II). La difosfina se utiliza convenientemente en exceso (referido a Pd), preferentemente en una cantidad de 0,2 hasta 5% en moles, también referida al compuesto halogenado (II).The palladium diphosphine complex, with catalytic action, is conveniently formed in situ , by reacting palladium elementally and finely distributed (for example, palladium on active carbon), a salt of Pd (II) (for example, chloride or acetate ), or a suitable complex of Pd (II) (for example, dichloro-bis (triphenylphosphine) -palladium (II), with diphosphine. Preferably, palladium is used in an amount of 0.02 to 0.2 mol% of Pd (II), or 0.5 to 2 mol% (Pd (0) (as Pd / C), always referred to the halogenated compound (II). Diphosphine is conveniently used in excess (referred to Pd), preferably in an amount of 0.2 to 5 mol%, also referred to the halogenated compound (II).
Como disolvente se pueden emplear tanto disolventes relativamente apolares tales como, por ejemplo, tolueno o xileno, como disolventes polares tales como, por ejemplo, acetonitrilo, tetrahidrofurano o N,N-dimetilacetamida.As a solvent, both relatively non-polar solvents such as, for example, toluene or xylene, can be used as polar solvents such as, for example, acetonitrile, tetrahydrofuran or N, N- dimethylacetamide.
Como base se utiliza, preferentemente, una base relativamente débil. Ésta no necesita ser soluble en el disolvente empleado. Resultan adecuados, por ejemplo, los carbonatos tales como carbonato sódico o carbonato de potasio, o acetatos tales como acetato sódico. Con la base mencionada en último lugar se han obtenido resultados especialmente adecuados.As a base, preferably, a base is used relatively weak This does not need to be soluble in the solvent employee. Suitable, for example, are carbonates such as sodium carbonate or potassium carbonate, or acetates such as sodium acetate With the last mentioned base they have obtained especially suitable results.
La temperatura de reacción se encuentra, preferentemente, entre 80 y 250ºC.The reaction temperature is found, preferably, between 80 and 250 ° C.
La presión de monóxido de carbono se encuentra, preferentemente, entre 1 y 50 bar.The carbon monoxide pressure is found, preferably, between 1 and 50 bar.
Los siguientes Ejemplos explican más detalladamente la realización del procedimiento según la invención.The following Examples explain more in detail the performance of the procedure according to the invention.
En 420 ml de N,N-dimetilacetamida se suspendieron 17,46 g (690 mmol) de hidruro sódico (al 95%). A 15ºC se agregaron, gota a gota, durante 2 h, 106,7 g (658 mmol) de 3-(trifluorometil)fenol. La solución de fenolato obtenida de esta forma se agregó, gota a gota, en el plazo de 2,5 h y bajo nitrógeno, a una solución de 162,4 g (1,097 mol) de 2,6-dicloropiridina en 330 ml de N,N-dimetilacetamida, calentada a 90ºC. Después de 3 h adicionales de reacción, se enfrió la mezcla a temperatura ambiente, se separó por filtración el cloruro sódico precipitado y se concentró el filtrado. El residuo se recogió con tolueno y ácido clorhídrico 0,1 N, la fase orgánica se lavó con una solución saturada de cloruro sódico y se concentró. El residuo oleoso (aprox. 200 g) se destiló al vacío.In 420 ml of N, N- dimethylacetamide 17.46 g (690 mmol) of sodium hydride (95%) were suspended. At 15 ° C, 106.7 g (658 mmol) of 3- (trifluoromethyl) phenol were added dropwise over 2 h. The phenolate solution obtained in this way was added, dropwise, within 2.5 h and under nitrogen, to a solution of 162.4 g (1.097 mol) of 2,6-dichloropyridine in 330 ml of N, N- dimethylacetamide, heated to 90 ° C. After an additional 3 h of reaction, the mixture was cooled to room temperature, the precipitated sodium chloride was filtered off and the filtrate was concentrated. The residue was taken up with toluene and 0.1 N hydrochloric acid, the organic phase was washed with a saturated sodium chloride solution and concentrated. The oily residue (approx. 200 g) was distilled under vacuum.
Rendimiento: 151,5 g (84%) de un aceite incoloro, contenido (CG) 99,8%.Yield: 151.5 g (84%) of a colorless oil, content (CG) 99.8%.
n_{D}^{20} = 1,5267n_ {D} 20 = 1.5267
MS, m z: 273/275, 238, 39MS, m z: 273/275, 238, 39
Bajo nitrógeno, se lavaron 7,68 g de dispersión de hidruro sódico (aprox. al 50% en aceite mineral) con pentano, agregando, a continuación, 100 ml de N,N-dimetilformamida. A temperatura ambiente, se agregaron, gota a gota, en un plazo de 30 min 21,92 g (135 mmol) de 3-(trifluorometil)fenol. La solución de fenolato obtenida de esta forma se agregó, gota a gota, en el plazo de 2 h y bajo nitrógeno, a una solución de 20,1 g (136 mmol) de 2,3-dicloropiridina en 80 ml de N,N-dimetilformamida, calentada a 120ºC. Después de 3 h de reacción, la mezcla se enfrió a temperatura ambiente, se separó por filtración el cloruro sódico precipitado y se concentró el filtrado. El residuo se extrajo con tolueno y ácido clorhídrico 0,1 N, la fase orgánica se lavó con una solución saturada de cloruro sódico y se concentró. El residuo oleoso se destiló al vacío.Under nitrogen, 7.68 g of sodium hydride dispersion (approx. 50% in mineral oil) was washed with pentane, then adding 100 ml of N, N- dimethylformamide. At room temperature, 21.92 g (135 mmol) of 3- (trifluoromethyl) phenol were added dropwise over 30 min. The phenolate solution obtained in this way was added, dropwise, within 2 h and under nitrogen, to a solution of 20.1 g (136 mmol) of 2,3-dichloropyridine in 80 ml of N, N - dimethylformamide, heated to 120 ° C. After 3 h of reaction, the mixture was cooled to room temperature, the precipitated sodium chloride was filtered off and the filtrate was concentrated. The residue was extracted with toluene and 0.1 N hydrochloric acid, the organic phase was washed with a saturated sodium chloride solution and concentrated. The oily residue was distilled under vacuum.
Rendimiento: 24,75 g (67%) de un aceite incoloro, contenido (CG) 99,7%.Yield: 24.75 g (67%) of a colorless oil, content (CG) 99.7%.
P.f._{18 mbar} = 145-148ºCP.f._ {18 mbar} = 145-148 ° C
n_{D}^{20} = 1,5282n_ {D} 20 = 1.5282
MS; m z: 273/275MS; m z: 273/275
En un autoclave se depositaron a temperatura ambiente 6,84 g (25 mmol) de 2-cloro-6-[3-(trifluorometil)fenoxi]-piridina (contenido 99,5%, preparada según el Ejemplo 1), 4,17 g (37,5 mmol) de 4-fluoroanilina, 2,92 g (27,5 mmol) de carbonato sódico, 0,27 g (0,25 mmol) de paladio/Carbón activo (Pd al 10%) y 0,32 g (0,75 mmol) de 1,4-bis(difenil-fosfino)butano (IV, n = 4, R^{8} = R^{9} = R^{10} = R^{11} = fenilo) en 25 ml de xileno. El autoclave se enjuagó con gas inerte, se agregaron a presión 5 bar de monóxido de carbono y se calentó a 200ºC. La presión de CO se elevó a 14,5 mol y la mezcla se agitó durante 16 h a 200ºC. Después de enfriar a temperatura ambiente y de la descarga de la presión, se mezcló la tanda de reacción con sendos 50 ml de xileno y agua y se filtró. La fase acuosa se extrajo con 25 ml de xileno y las fases orgánicas combinadas se lavaron con 30 ml de agua. Por medio de CG se determinó la composición del producto disuelto. Se encontraron 92,1% del compuesto del título (amida), 1,9% de educto y 6,0% de productos secundarios (3,1% de3 amina secundaria, formada por sustitución directa de Cl por la anilina, y 2,9% de 2-[3-(trifluorometil)fenoxi]piridina, formada por hidrogenó-lisis).In an autoclave they were deposited at temperature ambient 6.84 g (25 mmol) of 2-Chloro-6- [3- (trifluoromethyl) phenoxy] -pyridine (99.5% content, prepared according to Example 1), 4.17 g (37.5 mmol) of 4-fluoroaniline, 2.92 g (27.5 mmol) carbonate sodium, 0.27 g (0.25 mmol) of palladium / active carbon (10% Pd) and 0.32 g (0.75 mmol) of 1,4-bis (diphenyl phosphino) butane (IV, n = 4, R 8 = R 9 = R 10 = R 11 = phenyl) in 25 ml of xylene. The autoclave was rinsed with inert gas, added to pressure 5 bar of carbon monoxide and heated to 200 ° C. The CO pressure was raised to 14.5 mol and the mixture was stirred for 16 h at 200 ° C. After cooling to room temperature and discharge of the pressure, the reaction mixture was mixed with 50 ml of Xylene and water and filtered. The aqueous phase was extracted with 25 ml of xylene and the combined organic phases were washed with 30 ml of Water. The composition of the product was determined using GC dissolved. 92.1% of the title compound (amide) was found, 1.9% of educt and 6.0% of secondary products (3.1% of 3 amine secondary, formed by direct replacement of Cl by aniline, and 2.9% of 2- [3- (trifluoromethyl) phenoxy] pyridine, formed by hydrogenolysis).
Después de separar por destilación el disolvente, se obtuvo el producto bruto (8,63 g) en forma de sólido amarillo.After distilling off the solvent, the crude product (8.63 g) was obtained as a solid yellow.
Para la purificación se cristalizó el producto bruto a partir de metilciclohexano.For purification the product crystallized crude from methylcyclohexane.
Rendimiento: 6,3 g (67%) de cristales incoloros.Yield: 6.3 g (67%) of crystals colorless
P.f.: 104-106ºCMp .: 104-106 ° C
MS, m z: 376 (M^{+}), 238MS, m z: 376 (M +), 238
Se procedió de la forma descrita en el Ejemplo 3, si bien en lugar de paladio/carbón activo, se utilizaron 17,5 mg (25 \mumol) de dicloro-bis(trifenilfosfin)-paladio(II). La presión de CO ascendió a 12,8 bar, la temperatura fue de 50ºC y la duración de la reacción de 17,7 h. Por medio de CG se determinó la composición de los productos disueltos en la fase de xileno. Se encontraron 96,0% del compuesto del título (amida) y 4,0% de productos secundarios (2,3% de amina secundaria, 1,7% de producto de hidrogenólisis).It was proceeded in the manner described in Example 3, although instead of palladium / active carbon, 17.5 mg (25 \ mumol) of dichloro-bis (triphenylphosphine) -palladium (II). The CO pressure was 12.8 bar, the temperature was 50 ° C and the reaction duration of 17.7 h. By means of CG it was determined the composition of the products dissolved in the xylene phase. He found 96.0% of the title compound (amide) and 4.0% of secondary products (2.3% secondary amine, 1.7% product of hydrogenolysis).
Se procedió de la forma descrita en el Ejemplo 4, si bien en lugar de 1,4-bis(difenilfosfin)butano se utilizó la misma cantidad molar de 1,3-bis(difenilfosfino)propano (IV, n = 3, R^{8} = R^{9} = R^{10} = R^{11} = fenilo). La presión de CO fue de 16 bar, la duración de reacción fue de 21,6 h. Mediante CG se determinó la composición de los productos disueltos en la fase de xileno. Se encontraron 98,9% del compuesto del título (amida), 0,1% de educto y 1,0% de productos secundarios (0,3% de amina secundaria y 0,7% de producto de hidrogenólisis).It was proceeded in the manner described in Example 4, yes well instead of 1,4-bis (diphenylphosphine) butane se used the same molar amount of 1,3-bis (diphenylphosphine) propane (IV, n = 3, R 8 = R 9 = R 10 = R 11 = phenyl). The pressure of CO was 16 bar, the reaction duration was 21.6 h. Through CG the composition of the products dissolved in the phase was determined of xylene. 98.9% of the title compound (amide) was found, 0.1% educt and 1.0% secondary products (0.3% amine secondary and 0.7% of hydrogenolysis product).
De forma análoga al Ejemplo 4, se hicieron reaccionar 6,84 g (25 mmol) de 3-cloro-2-(3-trifluorometil)fenoxi-piridina (preparada según el Ejemplo 2), 4,84 g (37,5 mmol) de 2,4-difluoroanilina, 2,92 g (27,5 mmol) de carbonato sódico, 17,5 mg (25 \mumol) de ç dicloro-bis-(trifenilfosfin)paladio(II) y 0,32 g (0,75 mmol) de 1,4-bis(difenilfosfino)butano en 25 ml de xileno, bajo una presión de CO de 15 bar, a 190-195ºC. La reacción fue de aprox. 80%. El procesamiento se llevó a cabo de la forma descrita en el Ejemplo 3. Se obtuvieron 6 g de producto bruto en forma de sólido cristalino amarillo. Para la purificación se cristalizó a partir de 50 ml de metilciclohexano.Similarly to Example 4, they were made react 6.84 g (25 mmol) of 3-Chloro-2- (3-trifluoromethyl) phenoxy-pyridine (prepared according to Example 2), 4.84 g (37.5 mmol) of 2,4-difluoroaniline, 2.92 g (27.5 mmol) carbonate sodium, 17.5 mg (25 µm) of ç dichloro-bis- (triphenylphosphine) palladium (II) and 0.32 g (0.75 mmol) of 1,4-bis (diphenylphosphine) butane in 25 ml of xylene, under a CO pressure of 15 bar, at 190-195 ° C. The reaction was approx. 80% He Processing was carried out in the manner described in Example 3. 6 g of crude product were obtained as crystalline solid yellow. For purification it was crystallized from 50 ml of methylcyclohexane.
Rendimiento: 3,25 g (33%) de sólido blancoYield: 3.25 g (33%) of white solid
P.f.; 157-159ºCP.f .; 157-159 ° C
MS, m z 394 (M^{+}), 266 (100%)MS, m z 394 (M +), 266 (100%)
Ejemplo comparativo 1Comparative example 1
Se procedió de la forma descrita en el Ejemplo 4, si bien en lugar de 1,4-bis difenilfosfino)butano, se utilizó la misma cantidad molar de trifenilfosfina. Después de un período de reacción de 15,5 h a 15 bar de presión de CO, se determinó por CG la composición de los productos disueltos en la fase de xileno. Se encontraron sólo 43,2% del producto deseado, pero 56,8% de educto que no había reaccionado.It was proceeded in the manner described in Example 4, although instead of 1,4-bis diphenylphosphine) butane, the same molar amount of triphenylphosphine After a reaction period of 15.5 h at 15 CO pressure bar, the composition of the products dissolved in the xylene phase. Only 43.2% were found of the desired product, but 56.8% of educt that there was reacted
Ejemplo comparativo 2Comparative example two
Se procedió de la forma descrita en el Ejemplo 4, si bien en lugar de 1,4-bis difenilfosfino)butano, se utilizó la misma cantidad molar de tri-n-butilfosfina. Después de un período de reacción de 15 h a 14 bar de presión de CO, se determinó por CG la composición de los productos disueltos en la fase de xileno. Se encontraron sólo trazas (0,4%) del producto deseado, pero 96,8% de educto que no había reaccionado.It was proceeded in the manner described in Example 4, although instead of 1,4-bis diphenylphosphine) butane, the same molar amount of tri-n-butylphosphine. After a reaction period of 15 h at 14 bar of CO pressure, was determined by CG the composition of the products dissolved in the phase of xylene. Only traces (0.4%) of the desired product were found, but 96.8% of educt who had not reacted.
Ejemplo comparativo 3Comparative example 3
Se procedió de la forma descrita en el Ejemplo 4, si bien en lugar de 1,4-bis difenilfosfino)butano, se utilizó la misma cantidad molar de 1,2-bis(difenilfosfino)etano. Después de un período de reacción de 20,2 h a 14,7 bar de presión de CO, se determinó por CG la composición de los productos disueltos en la fase de xileno. Se encontraron sólo trazas (2,2%) del producto deseado, pero 97,7% de educto que no había reaccionado.It was proceeded in the manner described in Example 4, although instead of 1,4-bis diphenylphosphine) butane, the same molar amount of 1,2-bis (diphenylphosphine) ethane. Then from a reaction period of 20.2 h at 14.7 bar of CO pressure, determined by CG the composition of the products dissolved in the xylene phase Only traces (2.2%) of the product were found desired, but 97.7% of educt that had not reacted.
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